Phthalocyanine compounds used in inks for ink-jet printing

ABSTRACT

Phthalocyanine compounds of Formula (1) have utility as colorants in inks for ink-jet printing, where Formula (1) represents: 
     
       
         M v Pc(SO 2 NHAr) x   Formula (1) 
       
     
     in which: 
     M represents a metal or H; 
     Pc represents a phthalocyanine nucleus; 
     Ar represents an aromatic moiety optionally substituted by one or more groups selected from an optional substituent or optionally substituted C 1-30 carbyl; 
     v is the valence of Pc divided by the valence of M; and 
     x is from 2.5 to 4.5.

This application is the national phase of international applicationPCT/GB99/02453 filed Jul. 28, 1999 which designated the U.S.

This invention relates to compounds, to ink compositions comprising themand to the use of such inks in ink jet printing (“IJP”). IJP is anon-impact printing technique in which droplets of ink are ejectedthrough a fine nozzle onto a substrate without bringing the nozzle intocontact with the substrate.

There are many demanding performance requirements for colorants and inksused in IJP. For example they desirably provide sharp, non-featheredimages having good water-fastness, light-fastness and optical density.The inks are often required to dry quickly when applied to a substrateto prevent smudging, but they should not form a crust over the tip of anink jet nozzle because this will stop the printer from working. The inksshould also be stable to storage over time without decomposing orforming a precipitate which could block the fine nozzle.

It is essential that colorants used in IJP have good solubility(preferably in aqueous systems) so they can be dissolved in an ink andfired from the ink-jet head without coming out of solution and blockingthe nozzle. Yet colorants that have good operability (i.e. high watersolubility) are likely to produce prints of poor water fastness due tothe same high water solubility. A significant challenge in designing newcolorants for IJP is to provide in the same molecule the apparentlymutually exclusive properties of good operability for the ink and yethigh water fastness for the print. This often requires the synthesis ofa colorant molecule of complex structure comprising many differentfunctional groups and such complex molecules can be expensive anddifficult to prepare in high yield.

It would be advantageous to provide colorants which overcome some or allof the preceding disadvantages.

Therefore according to the present invention there are provided one ormore compounds of Formula (1) and salts thereof:

M_(v)Pc(SO₂NHAr)_(x)  Formula (1)

in which:

M represents a metal or H;

Pc represents a phthalocyanine nucleus;

Ar represents an aromatic moiety optionally substituted by one or moregroups selected from an optional substituent or optionally substitutedC₁₋₃₀carbyl;

v is the valence of Pc divided by the valence of M; and

x is from 2.5 to 4.5.

The applicant has discovered that the above phthalocyanine compoundshave particular utility as colorants for use in IJP. For example theycan produce IJ prints which exhibit good optical density, waterfastness, light fastness and/or a particularly attractive cyan shade.They are particularly useful for formulating IJP inks comprising a resincomponent.

The compounds of the present invention described herein include allchemical and physical forms thereof (such as those described herein).Preferred compounds are those which are IJP-effective.

The terms ‘optional substituent’ and/or ‘optionally substituted’ as usedherein (unless followed by a list of other substituents) signifies theone or more of following groups (or substitution by these groups):carboxy, sulpho, formyl, hydroxy, amino, imino, nitrilo, mercapto,cyano, nitro, halo, methyl and/or methoxy; and includes all directcombinations of a plurality (preferably two) of these groups (e.g. aminoand sulphonyl combined are sulphamoyl). Preferred optional substituentscomprise: carboxy, sulpho, hydroxy, amino, mercapto, cyano, halo, methyl(optionally substituted by one or more halo) and/or methoxy (optionallysubstituted by one or more halo).

The term ‘carbyl’ as used herein denotes any organic radical moietywhich comprises one or more carbon atoms and optionally one or moreother heteroatoms preferably selected from: hydrogen, phosphorus, halo,nitrogen, oxygen and/or sulphur, more preferably from hydrogen,nitrogen, oxygen and/or sulphur. The term ‘hydrocarbyl’ as used hereindenotes any radical moiety which comprises one or more hydrogen atomsand one or more carbon atoms. Most preferably ‘carbyl’ moieties compriseone or more of the following carbon containing moieties (includingcombinations thereof in the same moiety): alkyl, alkoxy, alkanoyl,carboxy, and/or formyl in optional combination with one or more of thefollowing hetero-atom containing moieties (including direct combinationsof a plurality (preferably two) of the hetero-atom moieties, (e.g. aminoand sulphinyl combined are sulphinamoyl): oxy, thio, sulphinyl,sulphonyl, amino, imino and/or nitrilo. Carbyl moieties may alsocomprise one or more double and/or triple carbon to carbon bonds and/oraromatic moieties. The optional hetero-atom and/or unsaturated groupsmay be located in any position in a carbyl moiety, optionallyinterrupting a chain.

The term ‘alkyl’ or its equivalent (e.g. ‘alk’) as used herein may bereadily replaced, where appropriate, by terms encompassing other similarmoieties (e.g. other hydrocarbyl moieties) such as those comprisingdouble bonds, triple bonds, and/or aromatic moieties (e.g. alkenyl,alkynyl and/or aryl) as well as multivalent species attached to two ormore substituents (such as alkylene). The term ‘halo’ as used hereinsignifies fluoro, chloro, bromo and iodo, preferably fluro and chloro.

When M is a metal it is preferably selected from Li, Na, K, Mg, Ca, Ba,Al, Si, Sn, Pb, Rh, Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu, morepreferably from Sc, Ti, Va, Cr, Mn, Fe, Co, Zn, Ni and Cu; especiallyfrom Ni and Cu, particularly Cu.

It will be appreciated that v (which denotes the stoichiometric ratio ofM to Pc) is the molar ratio which produces a stable complex. It canreadily be determined from the relative valences of Pc and M (e.g.v=Pc/M). Preferably, where Pc can be represented as a radical moiety offormula (2):

(where the valence of Pc is 2) then v is inverse half the valence of M.

It will also be appreciated that because of the nature of thepreparation of compounds of the present invention, in general they mayexist as a mixture of different compounds. Thus in Formula (1) thevalues for v and x may represent averages for the mixture. Insofar aspurification techniques will allow, it is preferred that the mixturecomprises one compound as the major component, more preferably themixture is substantially free of other compounds of Formula (1).

Preferably x is from 2.8 to 4.2, more preferably from 3.0 to 4.0, mostpreferably 3 or 4.

In the plurality of —SO₂NHAr groups attached to the Pc nucleus, the Argroup when substituted may be independently substituted by differentsubstituents on each Ar group.

Preferably Ar represents an aromatic moiety, more preferably aryl, mostpreferably phenyl, where the aromatic moiety is optionally substitutedby one or more C₁₋₃₀hydrocarbyl groups optionally interrupted by one ormore bivalent radical moieties selected from —O—; —CO—; —OCO—; —COO—;—S—; —SO— and —SO₂.

Preferred compounds of Formula (1) are those in which:

M is Cu or Ni,

Ar is a aryl group optionally substituted by one or more groups selectedfrom: halo; cyano, nitro, optionally substituted C₁₋₁₈hydrocarbyl;COOR¹; OCOR¹; COR¹; COCOR¹; SO₂R¹; SO₂OR¹; OSO₂R¹; NHCOR¹ and CONHR¹;where R¹ independently represents H or optionally substitutedC₁₋₁₈hydrocarbyl; and any of the above hydrocarbyl groups mayindependently be optionally interrupted by one or more of —O—; —CO—;—OCO—; —COO—; —S—; —SO— and —SO₂.

More preferred compounds of Formula (1) are those in which:

M is Cu,

Ar is phenyl optionally substituted by one or more groups selected from:halo; cyano, nitro, optionally substituted C₁₋₁₂alkyl; optionallysubstituted C₁₋₁₂alkenyl; optionally substituted C₁₋₁₂alkynyl;optionally substituted aryl; (optionally fused to the aryl ring to/formpolycyclic aromatic system); COOR¹; OCOR¹; COR¹; COCOR¹; SO₂R¹; SO₂R¹;OSO₂OR¹; NHCOR¹ and CONHR¹; where R¹ independently represents H oroptionally substituted C₁₋₁₂alkyl; optionally substituted C₁₋₁₂alkenyl;optionally substituted C₁₋₁₂alkynyl; and any of the above alkyl, alkenyland alkynyl groups may independently be optionally interrupted by one ormore of —O—; —CO—; —OCO—; —COO—; —S—; and —SO₂.

Most preferred compounds of Formula (1) are those in which:

M is Cu,

Ar is phenyl optionally substituted by one or more groups selected from:halo; cyano, nitro, optionally substituted C₁₋₁₈alkyl; COOR¹; OCOR¹;COR¹; COCOR¹; where R¹ independently represents H or optionallysubstituted C₁₋₁₂alkyl; any of the above alkyl groups may independentlybe optionally interrupted by one or more of —O—; —CO—; —OCO—; and —COO—.

Specific compounds of Formula (1) are selected from the compoundexemplified herein and any IJP-effective forms thereof.

Optionally compounds of the present invention may be dyes, preferablywater soluble dyes. However if dyes of the present invention are to beformulated in polymer containing inks (see below) they are optionallyinsoluble in water but soluble in the (water-dissipatable) polymer. Suchdyes are preferably free from carboxy and sulpho groups, and morepreferably are disperse or solvent-soluble dyes. Disperse and solventsoluble dyes are distinct from pigments in that pigments are insolublein organic solvents and polymers whereas disperse and solvent solubledyes are soluble in organic solvents and polymers.

Any radical group mentioned herein as a substituent refers to amonovalent radical unless otherwise stated. A group which comprises achain of three or more atoms signifies a group in which the chain may bestraight or branched or the chain or any part of the chain may form aring. Substituents may replace any H attached to an atom in the ring(e.g. Pc nucleus) or chain which is chemically suitable and may belocated at any available position on the ring or chain. Preferably thesubstituents on the Pc nucleus are positioned so that none of its phenylmoieties have more than one substituent. The total number of certainatoms is specified herein for certain substituents, for exampleC_(1-m)alkyl, signifies an alkyl group having from 1 to m carbon atoms.

Unless the context clearly indicates otherwise, as used herein pluralforms of the terms herein are to be construed as including the singularform and vice versa.

The term ‘IJP effective’ (for example with reference to the inks,compositions, ingredients, substituents and/or compounds describedherein) will be understood to mean effective for use in ink-jet printingby for example: providing desirable properties to the ink, beingcompatible with any inert carriers and/or diluents suitable forformulating such inks, being compatible with ink jet printers and/orcapable of being ink-jet printed. In relation to the processes describedherein effective compounds are those which will undergo the specifiedreactions to form the compounds of the present invention. Preferablycompounds acceptable for use in IJP are Ames negative.

It will be appreciated compounds of Formula(1) may exist in manydifferent physical and chemical forms which also form part of thepresent invention. These forms may comprise any of the following(including mixtures thereof and combinations thereof in the samemolecular moiety): salts, stereoisomers (e.g. enantiomers,diastereoisomers, geometric isomers, tautomers and/or conformers),zwitterions, polymorphic forms (e.g. phases, crystalline forms,amorphous forms, solid solutions and/or interstitial compounds);complexes (e.g. in addition to the metal Pc complexes described herein,chelates, solvates, hydrates and/or complexes with any other suitableligand) and/or isotopically substituted forms (optionally radio-active,e.g. used as means for selective imaging of the compounds and/or inkscontaining them and/or as tools to investigate their mode of action inIJP).

Compounds of Formula (1) may have many uses other than IJP. For exampleas well as colorants for IJP inks, compounds of the present inventionmay be used as intermediates in the preparation and/or purification ofother compounds of Formula (1) and/or as research tools and/ordiagnostic aids in relation to IJP.

The term ‘colorant’ as used herein includes both dyes and pigments.Colorants are not limited to materials which solely provide colour inthe visible region of the electromagnetic (EM) spectrum but includematerials (which may be visibly colourless or weakly coloured) whichattenuate radiation in other regions of the EM spectrum invisible to thenaked eye [e.g. ultra-violet (UV) and/or infra-red (IR) absorbers].Compounds of the present invention may exhibit such colorant propertiesoutside the visible region.

Compounds of Formula (1) may be prepared by the methods described belowand by other suitable methods analogous to those described in the artfor similar phthalocyanine compounds. A preferred method for preparingone or more compounds of Formula (1) comprises the following steps:

(i) condensing one or more compounds of Formula (3)

M_(v)Pc(SO₂Cl)_(x)  Formula(3)

 with an amine of formula NH₂Ar;

(ii) treating the adduct from step (i) with a base, to produce one ormore compounds of Formula (1);

where v, x, M, Pc, and Ar are as represented herein.

Preferably in step (i) the amine is present in approximately xequivalents to the amount of phthalocyanine compound.

Preferably in step (ii) the base comprises sodium hydroxide and the pHof the mixture may be adjusted to be from 7.0 to 9.0, preferably 8.0.

Compounds of Formula (3) may be prepared using known methods. Apreferred method preparing these compounds comprises heating (preferablyfor about 1 to about 24 hours), a metal-free or metal containingphthalocyanine (optionally comprising an average of two to four sulphogroups per molecule) with chlorosulphonic acid, preferably at atemperature above 60° C., more preferably above 100° C., most preferablyfrom 120° C. to 165° C. Optionally this may be followed cooling,preferably to a temperature from 30° C. to 50° C. The phthalocyanine isthen heated with PCI₃ (conveniently for about 4 to about 6 hours),preferably at lower temperature than with the chlorosulphonic acid, morepreferably from 80° C. to 105° C.

The reactions leading to the formation of the present compounds may beperformed under conditions that have been described in the art andcompounds of Formula (1) may be isolated by known methods such as spraydrying or precipitation followed by filtration.

In a further aspect of the present invention there is provided an inkwhich is effective for use in ink jet printing, the ink comprising afluid medium, (optionally a liquid) and a colorant (preferably a dye)comprising one or more compounds of the present invention as definedherein.

Preferably the ink of the present invention comprises:

(a) from 0.01 to 30 parts of a compound of Formula (1); and

(b) from 70 to 99.99 parts of a liquid medium or a low melting pointsolid medium; wherein all parts are by weight and the number of parts of(a)+(b)=100.

The number of parts of component (a) is preferably from 0.1 to 20, morepreferably from 0.5 to 15, and especially from 1 to 5 parts. The numberof parts of component (b) is preferably from 99.9 to 80, more preferablyfrom 99.5 to 85, especially from 99 to 95 parts.

When the medium is a liquid, preferably component (a) is completelydissolved in component (b). Preferably component (a) has a solubility incomponent (b) at 20° C. of at least 10%. This allows the preparation ofconcentrates which may be used to prepare more dilute inks and reducesthe chance of the colorant precipitating if evaporation of the liquidmedium occurs during storage. If desired further colorants may be addedto the ink to produce the desired colour or shade, although if a cyanink is desired this is not normally necessary because of the strong,attractive cyan colour of the compounds of the present invention.

Preferred liquid media include water, a mixture of water and an organicsolvent and an organic solvent free from water. When the mediumcomprises a mixture of water and an organic solvent, the weight ratio ofwater to organic solvent is preferably from 99:1 to 1:99, morepreferably from 99:1 to 50:50 and especially from 95:5 to 80:20.Preferably the organic solvent comprising the mixture of water andorganic solvent is a water-miscible organic solvent or a mixture of suchsolvents. The liquid medium may comprise water and preferably two ormore, more preferably from 2 to 8, water-soluble organic solvents.

Preferred water-miscible organic solvents comprise:

C₁₋₆-alkanols, preferably methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-pentanol, cydopentanol and/orcyclohexanol;

amides, preferably linear amides, more preferably dimethylformamideand/or dimethylacetamide;

ketones and/or ketone-alcohols, preferably acetone, methyl ether ketone,cyclohexanone and/or diacetone alcohol;

water-miscible ethers, preferably C₂₋₄ethers, more preferablytetrahydrofuran and/or dioxane;

alkylene glycols or thioglycols preferably containing a C₂-C₁₆ alkylenegroup, more preferably diols such as C₂₋₁₂diols (for examplepentane-1,5-diol, ethylene glycol, propylene glycol, butylene glycol,pentylene glycol, hexylene glycol and/or thiodiglycol) and/oroligo-and/or poly-(alkyleneglycols and/or thioglycols) for examplediethylene glycol, thiodiglycol, triethylene glycol, polyethyleneglycol, polypropylene glycol and/or polyols, e.g. glycerol and1,2,6-hexanetriol;

triols, preferably glycerol and/or 1,2,6-hexanetriol;

lower alkyl glycol and polyglycol ethers, e.g. C₁₋₄alkyl ethers ofdiols, preferably monoC₁₋₄alkyl ethers of C₂₋₁₂diols: {for example2-methoxyethanol; 2-(2-methoxyethoxy)ethanol;2-(2-ethoxyethoxy)-ethanol; 2-(2-butoxyethoxy)ethanol;3-butoxypropan-1-ol; 2-[2-(2-methoxyethoxy)ethoxy]ethanol;2-[2-(2-ethoxyethoxy)-ethoxy]ethanol and/or ethyleneglycol monoallylether};

cyclic amides, e.g. optionally substituted pyrollidones, preferably2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,caprolactam and/or 1,3-dimethylimidazolidone; cyclic esters, preferablycaprolactone;

sulphoxides, preferably dimethyl sulphoxide and/or sulpholane; and/or

mixtures containing two or more of the aforementioned water-miscibleorganic solvents.

More preferred water-soluble organic solvents are selected from: cyclicamides (e.g. 2-pyrrolidone, N-methyl-pyrrolidone andN-ethyl-pyrrolidone); diols, (e.g. 1,5-pentane diol, ethyleneglycol,thiodiglycol, diethyleneglycol and triethyleneglycol);

C₁₋₆-alkyl mono ethers of C₂₋₆-alkylene glycols;

C₁₋₄alkyl ethers of diols (e.g. 2-methoxy-2-ethoxy-2-ethoxyethanol);

C₁₋₆-alkyl mono ethers of poly(C₂₋₆-alkylene glycols); and

mixtures thereof.

One preferred liquid medium comprises: from 75 to 95 parts water; andfrom 25 to 5 parts in total of one or more solvents selected from:diethylene glycol, 2-pyrrolidone, thiodiglycol, N-methylpyrrolidone,cyclohexanol, caprolactone, caprolactam and pentane-1,5-diol; where theparts are by weight and the sum of the parts of water and solvent totals100.

Another preferred liquid medium comprises: from 60 to 80 parts water;from 2 to 20 parts diethylene glycol; and from 0.5 to 20 parts in totalof one or more solvents selected from: 2-pyrrolidone,N-methylpyrrolidone, cyclohexanol, caprolactone, caprolactam,pentane-1,5diol and thiodiglycol; where the parts are by weight and thesum of the parts of water, glycol and other solvent(s) totals 100.

Examples of further IJP-effective media for inks of the presentinvention comprise a mixture of water and one or more organic solventsare described in U.S. Pat. Nos. 4,963,189, 4,703,113, 4,626,284 and EP0425150-A.

When the liquid medium comprises an organic solvent free from water,(i.e. less than 1% water by weight) the solvent preferably has a boilingpoint of from 30° to 200° C., more preferably of from 40° to 150° C.,especially from 50 to 125° C. The organic solvent may bewater-immiscible, water-miscible or a mixture of such solvents.Preferred water-miscible organic solvents comprise any of thosedescribed above and mixtures thereof.

Suitable water-immiscible organic solvents comprise: aliphatichydrocarbons;

chlorinated hydrocarbons (for example dichloromethane);

aromatic hydrocarbons, e.g. toluene, xylene, naphthalene,tetrahydronaphthalene and methyl naphthalene;

chlorinated aromatic hydrocarbons, e.g. chlorobenzene, fluorobenzene,chloronaphthalene and bromonaphthalene;

esters, e.g. butyl acetate, ethyl acetate, methyl benzoate, ethylbenzoate, benzyl benzoate, butyl benzoate, phenylethyl acetate, butyllactate, benzyl lactate, diethyleneglycol dipropionate, dimethylphthalate, diethyl phthalate, dibutyl phthalate, di (2-ethylhexyl)phthalate;

alcohols having six or more carbon atoms, e.g. hexanol, octanol, benzylalcohol, phenyl ethanol, phenoxy ethanol, phenoxy propanol and phenoxybutanol;

ethers (for example diethyl ether), preferably those ethers having atleast 5 carbon atoms, more preferably C₅₋₁₄ ethers, e.g. anisole andphenetole; nitrocellulose, cellulose ether, cellulose acetate; low odourpetroleum distillates; turpentine; white spirits; naphtha;isopropylbiphenyl; terpene; vegetable oil; mineral oil; essential oil;and natural oil;

and mixtures of any two or more thereof.

Benzyl alcohol is an especially preferred water-immiscible solvent.

When the liquid medium comprises a water-immiscible organic solvent,preferably it comprises a polar solvent (for example a C₁₋₄alkanol) toenhance the solubility of the dye in the liquid medium. It is especiallypreferred that where the liquid medium is an organic solvent free fromwater it comprises a ketone (especially methyl ethyl ketone) and/or analcohol (especially a C₁₋₄alkanol, more especially ethanol or propanol).

The organic solvent free from water may be a single organic solvent or amixture of two or more organic solvents. It is preferred that when themedium is an organic solvent free from water it is a mixture of 2 to 5different organic solvents. This allows a medium to be selected whichgives good control over the drying characteristics and storage stabilityof the ink.

Ink media comprising organic solvent free from water are particularlyuseful where fast drying times are required and particularly whenprinting onto hydrophobic and non-absorbent substrates, for exampleplastics, metal and glass.

Preferred low melting solid media have a melting point in the range from60° C. to 125° C. Suitable low melting point solids include long chainfatty acids or alcohols, preferably those with C₁₈₋₂₄chains, andsulphonamides. The compound of Formula (1) may be dissolved in the lowmelting point solid or may be finely dispersed in it.

The compounds of the present invention have particular utility in inksin which component (b) comprises water and a water dissipatable polymer.The water-dissipatable polymer preferably bears ionised carboxy and/orsulphonate groups, especially ionised sulphonate groups, because theseassist water dissipatability of the polymer. Such groups can be chainpendant and/or terminal.

Preferably the water dissipatable polymer is selected from one or morepolyester, polyacrylate, polyurethane and mixtures thereof. Optionallythe water dissipatable polymer may also comprise a colorant, (e.g. adye) in the polymer chain. The optional colorant may chain extend and/orchain terminate the polymer and/or be incorporated within the polymerchain. One or more compounds of the present invention may comprise thecolorant used to form those water dissipatable polymers which areoptionally coloured. Preferably the polymer has an average molecularweight below 25,000 daltons. Preferably the water dissipatable polymerscan be prepared and have the properties, as described in the applicant'spublished patent applications for such polymer inks WO 9706217, WO9814523 WO 9814524 and WO 9814525 and in the applicant's co-pendingapplications for: polyester containing inks GB 9805782.1, GB 9806809.1,GB 9806810.9, GB 9808812.5, PCT/GB98/01583 and PCT/GB98/01584;polyurethane containing inks: GB 9806788.7, GB 9806789.5, GB 9806790.3and GB 9806791.1; and polyacrylic containing inks GB 9806793.7.

Preferably inks comprising a water dissipatable polymer are prepared bymixing together (i) a solution of the compound(s) of the presentinvention in a water-immiscible solvent and (ii) a mixture of a water-dissipatable polymer, water-miscible solvent and optionally water.Equally the inks may be prepared by mixing together (i) a solution ofthe compound(s) of the present invention in a mixture of awater-miscible solvent and a water-immiscible solvent and (ii) awater-dissipatable polymer and optionally water. In either case, ifthere is no water in component (ii) the water may be added to themixture of (i) a (ii) subsequently to give an ink according to theinvention. However it is preferred for component (ii) to contain water.These processes lead to particularly good up-take of the compound(s) ofthe present invention by the polymer to give intensely coloured inks.

The amount of the compound(s) of the present invention andwater-dissipatable polymer contained in the ink will vary according tothe depth of shade required. Typically, however, the ink will comprise:

(a) from 0.5 to 15 parts, more preferably 0.8 to 10 parts, especially 1to 5 parts in total of the compound(s) of the present invention;

(b1) from 0.2 to 25 parts, more preferably 2 to 15 parts of awater-dissipatable polymer;

(b2) from 40 to 90 parts, more preferably from 50 to 80 parts of water;and

(b3) from 0 to 60 parts, more preferably 0 to 40 parts of organicsolvent;

where all parts are by weight and the total number of parts of(a)+(b1)+(b2)+(b3) add up to 100. The number of parts of thewater-dissipatable polymer is calculated on a 100% solids basis. Forexample 50 g of a 20% solids polymer is taken as 10 g of polymer.

The optional organic solvent, mentioned in (b3) above, present in thesepolymer containing inks may contain an organic solvent and this may be amixture of organic solvents. In a preferred embodiment the ink containsan organic solvent consisting of a water-miscible organic solvent and awater-immiscible organic solvent (such as one or more of those describedpreviously).

Component (b3) of the above mentioned polymer containing inks preferablycomprises;

(i) 5% to 50% of a water-immiscible alcohol having at least six carbonatoms, more preferably benzyl alcohol; and

(ii) 50% to 95% of a water-miscible solvent comprising:

(1) a cyclic ester or cyclic amide, more preferably an optionallysubstituted pyrrolidone, [e.g. 2-pyrrolidone, dimethyl pyrrolidone,N-methyl-2-pyrrolidone, N-ethyl-2- pyrrolidone andN-(2-hydroxyethyl)-2-pyrrolidone and mixtures thereof];

(2) a water-miscible C₁₋₆-alkyl mono ether of a C₂₋₆-alkylene glycol orC₁₋₆-alkyl mono ether of poly(C₂₋₆-alkylene glycol); or

any mixtures of (1) and (2). All percentages are by weight and add up to100%.

The water-immiscible solvent preferably has a solubility in water at 20°C. of up to 50 g/l. The water-miscible solvent preferably has asolubility in water at 20° C. of more than 50 g/l.

The ratio of water-miscible organic solvent to water-immiscible organicsolvent is preferably 19:1 to 1:1, more preferably 8:1 to 1:1,especially 5:1 to 1:1.

A further feature of the invention provides a composition comprising awater-dissipatable polymer and a compound of Formula (1). In thesecompositions the preferred water-dissipatable polymers and compounds ofthe invention are as described herein. Such compositions may bedissipated in water and optionally mixed with further ingredients togive in ink, for example with one or more organic solvents. Thesecompositions preferably comprises (a) 0.125 to 40 parts of a colorant(more preferably the colorant consists only of compounds of the presentinvention); and (b) 99.875 to 60 parts of the water-dissipatablepolymer, where the total number of parts of (a) and (b) adds up to 100.

The inks of the present invention may also contain additional componentsconventionally used in inks for IJP, for example viscosity and surfacetension modifiers, corrosion inhibitors, biocides, kogation reducingadditives and surfactants which may be ionic or non-ionic.

Preferably for use in the inks of the present invention compounds ofFormula 1 are dyes. Use of dyes has advantages over the use of pigmentsin that less dye is usually required than would be the case for apigment, expensive milling is avoided, the inks are less likely to forma precipitate on standing, a far greater variety of shades are availableand the resultant prints have good transparency.

A valuable feature of inks of the invention is the low tendency forblocking the nozzles of thermal ink jet printers. This is particularlydifficult to achieve for polymer containing inks. Many other waterdispersible polymer inks work poorly or even not at all in thermalprinters. The inks of the invention (including those that comprise thewater dissipatable polymers) form discrete droplets on the substratewith little tendency for diffusing. Consequently sharp images can beobtained, resulting in excellent print quality and little if any bleedbetween colours printed side-by side. The inks of the present inventionbenefit from good light- and water-fastness.

A further aspect of the invention provides a process for printing animage on a substrate comprising applying to the substrate by means of anink jet printer, an ink of the present invention as defined herein.

The ink jet printer preferably applies the ink to the substrate in theform of droplets which are ejected through a small orifice onto thesubstrate. Preferred ink jet printers are piezoelectric ink jet printersand thermal ink jet printers. In thermal ink jet printers, programmedpulses of heat are applied to the ink in a reservoir (e.g. by means of aresistor adjacent to the orifice) thereby causing the ink to be ejectedin the form of small droplets directed towards the substrate duringrelative movement between the substrate and the orifice. Inpiezoelectric ink jet printers the oscillation of a small crystal causesejection of the ink from the orifice.

A further aspect of the present invention provides a substrate which hasapplied thereon an ink of the present invention as defined herein and/orone or more compounds of the present invention as defined herein.

The substrate preferably comprises paper, plastic, a textile, metal orglass, more preferably paper, an overhead projector slide or a textilematerial, especially paper.

Preferred papers are plain or treated papers which may have an acid,alkaline or neutral character.

Preferably the ink and/or compounds of the present invention have beenapplied to the substrate by a printed process, more preferably theprocess of the present invention as defined herein.

When the substrate is a textile material the ink according to theinvention is preferably applied thereto by:

i) applying the ink to the textile material using an ink jet printer;and

ii) heating the printed textile material at a suitable temperature,preferably from 50° C. to 250° C., to fix the ink on the material.

Preferred textile materials are natural, synthetic and semi-syntheticmaterials. Examples of preferred natural textile materials include wool,silk, hair and cellulosic materials, particularly cotton, jute, hemp,flax and linen. Examples of preferred synthetic and semi-syntheticmaterials include polyamides, polyesters, polyacrylonitriles andpolyurethanes.

Preferably the textile material has been treated with an aqueouspre-treatment composition comprising a thickening agent and optionally awater-soluble base and a hydrotropic agent and dried prior to step i)above.

The pre-treatment composition preferably comprises a solution of thebase and the hydrotropic agent in water containing the thickening agent.Particularly preferred pre-treatment compositions are described morefully in EP 0534660-A.

A further feature of the present invention is a cartridge suitable foruse in an ink jet printer containing an ink according to the invention.Also there is provided an ink jet printer containing an ink according tothe invention.

The invention is further illustrated by the following Example in whichall parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

Preparation of

a) Preparation of CuPc(SO₂Cl)₄

Copper phthalocyanine (14.4 g) was added in portions to stirredchlorosulphonic acid (50 ml) keeping the temperature at or below 40° C.The reaction mixture was heated to 150° C. over one hour, at whichtemperature it was stirred for 6 hours.

The mixture was allowed to cool to 65° C. and phosphorus trichloride(8.75 ml) was added dropwise. The reaction mixture was slowly heated to90° C. and maintained at this temperature for 16 hours, then cooled toabout 10° C. and poured onto a mixture of ice and water (350 ml). Theblue, precipitated product was collected by filtration at reducedpressure and washed with ice-cold water to obtain a paste which was useddirectly in step (c).

4-Nitrobenzoyl chloride was reacted with 2-(2-methoxyethoxy) ethanol indichloromethane in the presence of triethylamine. The nitro group in theresultant product was reduced by catalytic hydrogenation to obtain theabove amine.

(c) Preparation of Title Dye

The product from stage (a) was added in portions to a suspension of theamine [26.3 g, prepared as described in step (b)] in water (300 ml) at40° C. and pH from 8.5 to 9.0. The reaction mixture was stirred for 30minutes at 40° C. and then heated to 80° C. for two hours whilst the pHwas maintained from 8.5 to 9.0. The reaction mixture was added to water(500 ml) then sodium chloride (10% w/v) was added and the pH of themixture was adjusted to 2.0 with concentrated hydrochloric acid. Theresultant precipitate was collected by filtration at reduced pressureand washed with acidified brine (5%, 500 ml). The solids were collectedby filtration under reduced pressure and purified by addition to ethylacetate to form a slurry from which the solids were again isolated byfiltration under reduced pressure to obtain as the product 21.4 g of thetitle dye (λ_(max)=672 nm).

Preparation of a Resin Component of an Ink (“the Resin”)

To a glass reactor fitted with distillation column and condenser werecharged the following ingredients: neopentyl glycol (15 g); diethyleneglycol (10 g); sodio-5-sulpho-isophthalic acid (10 g); hexane-1,6-diol(10 g); methoxy PEG 750 (10 g); sodium acetate (0.2 g); isophthalic acid(22.5 g); and Fascat 4101 (0.05 g). The contents were heated withstirring to a reaction temperature of 210° C. until the mixture wasclear and the acid value was <10 mgKOH per g. At this point the afurther 22.5 g of isophthalic acid and 0.05 g of Fascat 4101 were addedto the reaction vessel and the temperature raised to 230° C. Thereaction was continued under reduced pressure until an acid value of 9.4mg KOH per g was obtained. The polymer was further characterised by ahydroxyl value of 12.8 mg KOH per g; ICI Cone and Plate Viscosity @ 125°C. of >500 poises and a T_(g) (onset) of 18° C. The number averagemolecular weight as determined by gel permeation chromatography (PSEquivalents) was 1800. The polymer obtained was readily dispersed inwarm distilled water to give a clear solution having a solids content of20% w/w (hereinafter referred to as the “Resin”).

Inks

The effectiveness in ink jet printing of compounds of Formula (1) wasdemonstrated as follows.

The dye of Example 1 (3 g) was dissolved in benzyl alcohol (10 g) and2-pyrrolidone (20 g). A solution (50 g) of the Resin (20% resin w/w, atpH 8.9) was dissipated in water (18 g). This resin solution was thenmixed with the dye solution and shaken to give a homogeneous ink whichwas stable for two months at room temperature.

This ink was printed onto the papers listed in below using a Olivetti JP450 ink jet printer to give cyan prints the properties of which aresummarised in the following table:

Paper OD LF WF XA 0.849 6.05 10 WC 0.730 4.73 9

where:

XA denotes Xerox Acid 4024 paper from Rank Xerox.

WC denotes Wiggins Conqueror High White Wove 100 gm⁻² paper from ArjoWiggins Appleton.

OD denotes the optical density of a print, measured using an X-Rite 938Spectrodensitometer. LF denotes light fastness, determined by the changein L.a.b coordinates as measured by an X-Rite 938 Spectrodensitometerafter the print has been irradiated (ΔE) for 100 hrs in a Atlas Ci35AWeatherometer. A low figure indicating high light-fastness. WF denoteswet fastness, determined by running water (0.5 ml) down lines of printat an angle of approximately 45° C. immediately after the lines had beenprinted. The prints were given a score of 1-10 where 1 indicates poorwet fastness and 10 indicates no detected ink run down (i.e. 100% waterfast).

Further inks may be prepared having the formulations described in tablesbelow. These inks may be applied to any suitable media (e.g. the papersgiven above) using an ink jet printer. In the tables R denotes the Resinprepared as described above, (comprising 20% solids and 80% water). Thenumber of parts by weight of the respectively the dye of Example 1 andthe Resin are shown in the columns headed Dye and R respectively. Thefollowing abbreviations are also used in the tables:

2P is 2-pyrollidone; ACE is acetone; AS is (NH₄)₂SO₄; BUT is butylcellosolve; BZ is benzyl alcohol; CAP is caprolactam; DEG is diethyleneglycol; DMB is diethyleneglycol monobutyl ether; FRU is fructose; GLY isglycerol; IPA is isopropyl alcohol; MA is CH₃NH₂; MEOH is methanol; MIBKis methylisobutyl ketone; NMP is N-methyl pyrollidone; PHO is K₂PO₄; Ris the Resin; SUR is Surfynol 465 (a surfactant); TDG is thiodiglycol;TEN is triethanolamine; and W is water.

TABLE I Dye W R BZ DEG 2P MIBK BUT 2.0 58 10 4 6 10 10 2.1 60.9 6 8 20 12 1.8 63.2 10 5 15 5 1.0 63 7 5 4 15 5

TABLE II Dye W R BZ DEG ACE IPA 2P MIBK 5.0 54 5 15 3 3 6 5 4 5.0 50 1520 10 5.0 70 10 6 2 2 1 4 2.0 62.7 5 10 7 3 10 5.4 49.6 4 20 2 1 15 3

TABLE III Dye W R BZ DEG NaOH 2P 3.0 61.8 10 5 5 0.2 15

TABLE IV Dye W R BZ ACE MEOH 2P MIBK BUT 2.4 51.6 5 4 5 6 20 5 1 3.363.7 12 5 5 2 6 3

TABLE V Dye W R BZ NaOH AS 2P MIBK BUT 1.1 61.9 12 9 0.5 0.5 9 5 1

TABLE VI Dye W R BZ DEG ACE AS 4.1 68.6 10 5 2 10 0.3

TABLE VII Dye W PG BZ DEG ACE IPA MEOH 2P MIBK 3.2 57.8 4 5 4 6 5 4 6 5

TABLE VIII Dye W R BZ NMP SUR TEN TDG FRU PHO DMB 1.5 63 10 5 0.15 0.520 0.9 63 5 10 20 0.5 0.2 2.2 67 10 10 3 2 6 9.0 34 15 19 17 0.5 0.95 55.4 54 12 5 17 7 2.1 65 15 5 5 0.1 0.2 2 0.5 0.1 5 2 56 10 10 5 12 5 1063 13 2 12

TABLE IX Dye W R BZ NMP SUR TEN TDG DMB MA CAP 3.1 64 10 8 0.3 15 0.28.0 40 15 15 15 5 2 5.0 57 10 11 10 6 1 8.0 42 20 15 8 5 2

TABLE X Dye W R BZ NMP FRU PHO DMB MA CAP 2.5 60 15 6 15 0.12 4 4.0 6710 10 4 1 4 0.2

What is claimed is:
 1. An ink comprising: i) a compound of Formula (1)and salts thereof: M_(v)Pc(SO₂NHAr)_(x)  Formula (1)  in which: Mrepresents a metal or H; Pc represents a phthalocyanine nucleus; Arrepresents an aromatic moiety optionally substituted by one or moregroups selected from the groups consisting of an optionally substituentor optionally substituted C₁₋₃carbyl; v is the valence of Pc divided bythe valence of M; and x is from 2.5 to 4.5; ii) water; and iii) a waterdissipatable polymer.
 2. An ink according to claim 1 wherein in thecompound of Formula (1): M is Cu or Ni, Ar is a aryl group optionallysubstituted by one or more groups selected from the group consisting ofhalo; cyano, nitro, optionally substituted C₁₋₁₈hydrocarbyl; COOR¹;OCOR¹; COR¹; COCOR¹; SO₂R¹; SO₂R¹; OSO₂R¹; NHCOR¹ and CONHR¹; where R¹independently represents H or optionally substituted C₁₋₁₈hydrocarbyl;and any of the above hydrocarbyl groups may independently be optionallyinterrupted by one or more of —O—; —CO—; —OCO—; —COO—; —S—; —SO—and—SO₂.
 3. An ink according to claim 1 or claim 2 wherein in the compoundof Formula (1): M is Cu; Ar is phenyl optionally substituted by one ormore groups selected from the group consisting of halo; cyano, nitro,optionally substituted C₁₋₁₂alkyl; optionally substituted C₁₋₁₂alkenyl;optionally substituted C₁₋₁₂alkynyl; optionally substituted aryl; COOR¹;OCOR¹; COR¹; COCOR¹; SO₂R¹; SO₂OR¹; OSO₂R¹; NHCOR¹ and CONHR¹; where R¹independently represents H or optionally substituted C₁₋₁₂alkyl;optionally substituted C₁₋₁₂alkenyl; optionally substitutedC₁₋₁₂alkynyl; and any of the above alkyl, alkenyl and alkynyl groups mayindependently be optionally interrupted by one or more of —O—; —CO—;—OCO—; —COO—; —S—; and —SO₂.
 4. An ink according to claim 1 wherein inthe compound of Formula (1): M is Cu, Ar is phenyl optionallysubstituted by one or more groups selected from the groups consisting ofhalo; cyano, nitro, optionally substituted C_(1-8 alkyl; COOR) ¹; OCOR¹;COR¹; COCOR¹; where R¹ independently represents H or optionallysubstituted C₁₋₈alkyl; and any of the above alkyl groups mayindependently be optionally interrupted by one or more of —O—; —CO—;—OCO—; and —COO—.
 5. An ink according to any one of the preceding claimscomprising: (a) from 0.5 to 15 parts of a compound of Formula (1) (b1)from 0.2 to 25 parts of a water-dissipatable polymer; (b2) from 40 to 90parts of water; and (b3) from 0 to 60 parts of organic solvent; whereall parts are by weight and the total number of parts of(a)+(b1)+(b2)+(b3) add up to
 100. 6. An ink which is effective for usein ink jet printing, the ink comprising a fluid medium and a colorantcomprising one or more compounds of Formula (1) according to claim
 1. 7.A compound of Formula (1) and salts thereof:M_(v)Pc(SO₂NHAr)_(x)  Formula (1) in which: M represents a metal or H;Pc represents a phthalocyanine nucleus; Ar represents an aryl groupcarrying at least one COOR¹ substituent where R¹ is a C₁₋₁₈ hydrocarbylinterrupted by one or more of —O—; —CO—; —OCO—; —COO—; —S—; —SO—and—SO₂; v is the valence of Pc divided by the valence of M; and x is from2.5 to 4.5.
 8. A process for printing an image on a substrate comprisingapplying to the substrate by means of an ink jet printer, an inkaccording to any one of claims 1 to
 6. 9. A substrate which has appliedthereon, an ink according to any one of claims 1 to
 6. 10. A cartridgesuitable for use in an ink jet printer containing an ink according toany one of claim 1 to
 6. 11. An ink according to claim 3 wherein theoptionally substituted aryl is fused to the phenyl ring to form apolycyclic ring system.
 12. A substrate which has applied thereon, oneor more compounds according to claim 7.